Process for the production of hydrocarbons



Dec. 3, 1940.

' i W. HERBERT PROCESS FOR THE PRODUCTYION OF HYDROCARBONS v Filed NOV. 24, 1957 t Atl'mmelis Patented Dec. 3, 1940 I PATENT oFFlcE PROCESS FOR THE PRODUCTION 0F BOCARB GNS Wilhelm Herbert, Frankfort-on-the-Main, Ger. many, assignor to American Lurgl Corporation, New York, yNrY., a corporation of New York Application November 24, 1937. Serial No. 176,373 In Germany December 2, 1936 (Cl. 261B- 449) This invention relates to the catalytic production of hydrocarbons.

The catalytic conversion of gases containing oxides of carbon and hydrogen into liquid hydrocarbons of higher molecular weight with several linkages chiefly of the olefin@ and paraln type, is performed with so-called synthesis gases in which the ratio of carbon monoxide to hydrogen is 1:2. In operating such synthesis on a manufacturing scale the object is to produce a gas with the highest possible degree oi' purity. For this reason, it is customary to produce a synthesis gas which contains up to 30% of carbon monoxide and 58 to 60% of hydrogen, so that the remainder consists of about 10 to 12% `of inert gases (CO2, Na and CHr), that is, gases taking no part in the reaction, for the Fischer- Tropsch benzine synthesis process under ordinary pressure (see ,Brennstoifchemia 1935, No. 1, pages 1'11). o

Experiments have also been performed with diluted synthesis gases in which a degree of dilution-referred to a 100% mixture of carbon monoxide and hydrogenof 20 to 40% is obtained by the addition of nitrogen, methane and carbon dioxideisee Journal of the Society of Chemical Industry, Japan, vol. 37,- No. 11,.pp. 704-615 B). The yields of liquid products obtained in these experiments, and expressed in cubic centimetres per cubic metre of the synthesis gas, are inferior to those from a highpercentage synthesis gas with the usual COzHz ratio of 1:2. On the contrary it was found that the extensively diluted gases have a very unfavorable efiect on the benzine synthesis, and that progressive dilution of the original gasis accompanied by the production of a gradually more volatile and lighter synthetic benzine (loc. cit. p. 7-11 B).

It has been ascertained in accordance with the present invention that the same, and even better, results can be obtained in the conversion of carbon monoxide and hydrogen into liquid hydrocarbons by the aid of the known catalysts employed in. the Fischer-Tropsch benzine-synthesis by increasing the content of inert gas constituents in the synthesis gases to a greater extent than usual, for example to over 20%, and performing the synthesis under a pressure exceeding that of the atmosphere (above 2 atmospheres for example) and at temperatures below those needed for the exclusive formation of methane. It is advisable, in these circumstances, to dilute the original gas to a greater extent as the working pressure is increased.

There are several possibilities to dilute the reaction gases according to the invention.

The well known synthesis of methanol by catalytic conversion of carbon monoxide and hydrogen-containing gases at temperatures above 5 250 C. and at pressures above 100 atmospheres gives an end gas after the formation of the known oxygen-containing products as alcohol, acetone, aldehyde which contains for example -25% CO, lil-% H2, 20-30% CHr, the rest being CO2 and 10 N2. Such a gas can be converted according to the invention in a second contact stage or stages in the presence of suitable catalysts at pressures between 1 to 200 atmospheres and at temperatures below 300 C., e. g. 180260 C. into hydro- 15 carbons of higher molecular weight, preferably of oleflne and paraffin type. Thus after the methanol synthesis a second synthesis for forming benzine at a pressure considerably exceeding the atmospheric pressure is arranged, whereby 20 known catalysts consisting, for example, of cobalt, thorium oxide and kieselguhr are employed.

Before employing the end gas of the methanol synthesis for a second synthesis according to the invention a part or all of the reaction products may be separated in known manner from the end gas. If necessary this end gas may be corrected with regard to its content of carbon monoxide and hydrogen by mixing with other suitable gases or by thermal decomposition of the methane or a. part thereof before using it in the second stage of synthesis.

A dilute synthesis gas can also be produced, according to the present invention, in an extremely simple manner by starting, in known manner, with a normal technical synthesis gas containing about 12% of inert gas constituents and bringing such gas into reaction, under a pressure not much diierent from atmospheric pressure by the aid of the known catalysts used in the Fischer- Tropsch benzine-synthesis, as describedfor example in Brennstoffchemie, 1932, No. 4, pp, 61 et seq. According to the invention, after removal of part, or all, of the reaction products, the resulting end gas-which is thus in a diluted condition with regard to its content of. carbon monoxide and hydrogen-is next compressed and is convertedin several stages, if desired-in a. second contact furnace, under elevated pressure, with the same known catalysts (such as 33% of 50 Co, 5% of ThO'.` and 61% of kieselguhr).

Various attempts have also been made to perform the benzine synthesis under elevated pressure (for example, 5 to 10 atmospheres) with the known synthesis gas containing only up to about the practicability of the whole process problemat-A ical.

It has now been ascertained that the benzine synthesis can be very satisfactorily performed under elevated pressurev (above 2 atmospheres,

. preferably above atmospheres) if the synthesis gases be employed in an extensively dilute condition, that is to say, with a content of more than 20% of inert constituents (CH4, CO2, Ili).

Most combustible or inert technical gases may be employed as diluents. Special advantages result from the employment, as admixtures. of such gases or vapors as can be easily removed from 'the end gases by the usual technical means, and therefore do not needlessly burden the attached apparatus for the separation of the reaction products. Such substances comprise CO2, H2O, alcohols, higher hydrocarbons, and so forth. It is also of advantage to employ, as diluents. substances (for example, CI-I4, CO2, and the like) which occur, in the reaction, as less desirable byproducts of the synthesis. In this manner it is possible, according to the relative proportions of the mixture, not only to facilitate the performance of the synthesis under pressure, but also to control the reaction to a certain extent. If higher hydrocarbons, such as benzine vapors, be added to the synthesis gas, the reaction can be modied in the direction of an increased formation of oil or paraffin, and the same applies to the addition of gas-oil vapors. Moreover, the addition of benzine v apors to the synthesis gas increases the working life of the catalyst -because an automatic extraction of the high-boiling substances which impair the activity of the catalyst, takesplace to a certain extent.

The present process is applicable, with particular advantage, when the further employment of the synthesis gaswhen freed from the reaction products-is contemplated, yfor instance, as illuminating gas or as original gas for the production of a further quantity of synthesis gases. In such case, the gas constituents lacking or present in insuiiicient amount in the e-nd gas may be added to the latter, as diluents, prior to the entry of the synthesis gases into the contact furnace. In this way, two effects are obtained, viz. improved conditions for the lreaction in the contact furnace, and the production of an end gas suitable for other useful purposes.

In a general way, it has been found that the content of admixed gases or vapors desirable in,

the interests of a smooth reaction may be the greater the higher the pressure employed for the reaction. The surprisingly favorable effect of dilute gases or vapors in performing the synthesis under pressure could not have been foreseen, inasmuch as, in performing the synthesis under normal pressure, the endeavor is to maintain the concentration Aof the actual synthesis gas ,at the highest possible level. In .operating at normal pressure with diluted' gases there is-as frequently described in the literature-an important diminution in the yield of liquid products.

The present process is also applicable in combination with existing plants operating with normal pressure by compressing and subjecting to synthesis under pressure, the end gases fromv a normal synthesis stage, which, after the removal of the reaction productshave become impover-v ished in unconverted synthesis gases. By this means, a far better total yield is obtained than by passing the diluted end gasesafter the removal of the reaction products-through a 'second contact furnace, at atmospheric pressure, in the manner heretofore customary.

In addition to the employment of 'the means lspecified in the foregoing, the principle underthe reaction after the complete removal of the reaction products and any surplus that may occur. There is no need to mix the fresh gas with that in circulation before their admission into the contact furnace, in fact, the incorporation of the fresh gas may be effected, with particular advantage, approximately midway of the reaction zone, or distributed by stages, over several reaction zones. In this way the reaction is more uniformly distributed over the contact furnace, whereas, otherwise the main reaction is concentrated in the gas-inlet side and gives rise to the risk of overheating and the intensified formation of undesired by-products.

Example I The originalgas for the synthesis had the composition:

N220%, CO2 7%, CHA 10%, CO 21% and H2 42% After passing this synthesis gas over a contact mass composed of Co 33%, ThOz 5% and kieselguhr 61%, at 190 C. and with a gas velocity of 1.6 N litres (=1.6 normal litres), the volume being calculated on a gas with (CO-l-Hz), per 1 grm. of Co in the contact mass, and per hour, a yield of 68 grms. of benzine, oil and paraiiin (i. e. liquid products) per N cubic metre (=1 normal cubic metre) of original gas was obtained when the operation was performed under normal (atmospheric) pressure. On carrying out the conversion in the same contact furnace at 12 atmospheres in accordance with the present invention a yield of 88 grms. of liquid hydrocarbons is obtained per N cubic metre when a lower temperature C., instead of 190 C.) coz-responding to the higher pressure is maintained. If the same original gas be converted with the same catalyst,V at a pressure of 60 atmospheres and a temperature of 174 C., the yield of the said liquid hydrocarbons is increased to 96 grms. per N cubic metre.

A further advantage of the present invention consists in that increasing the pressure in the course of the catalysis greatly facilitates the separation of the valuable reaction products. 'I'he separation of other substances from the end gases of the synthesis stages operating under normal or elevated pressure, and also the residual gases remaining after the final stage of the synthesis, is also substantially facilitated (if such separation is to be effected). Thus, for'example, by employing la higher pressure beyond the first stage, or portion, of the catalysis, all the 011 anda largeportion of the benzine can be separated-or even the whole of the benzine and of the gas oil, if the pressure be raised suiciently- 75 Astages if desired) or by means of aband adsorption apparatus, each of which can be used singly, two-by-two, in several groups, orall together in combination. The pressure mam also be increased between the two parts, or individual stages, with a view to especially facilitating the separation of the reaction products, and by allowing expansion to occur prior to entering the next portion, or next reaction stage, in which case it is of advantage to recover in known manner, the energy liberated by the expansion with a view to lessening the power consumption of the compressors.

The pressure in the pressure stage of the catalysis may vary in degree. It is advisable to employ such a high pressure that the partial pressure of the gas constituents (carbon monoxide and hydrogen) coming. into reaction in these stages correspondsatieast, to the partial Ypressure in the original gas in the synthesis at atmospheric pressure. If, for example, the end gas from the first stage-conducted at approximately 1 atmospherestill contains 30% of (CO-l-Ha) ,of the 90% (CO+Hz) present in the original gas, then, according tothe invention, the following stage is conductedunder a pressure of, for example, at least 3 atmospheres. In the event of there being a third stage with a content of, for example 20% (CO-l-Hn) the pressure will, in accordance vwith the invention, be above 41/2 atmospheres (for example, -6 atmospheres).

The reaction temperature in the pressure stage, or stages, of the catalysis, may be the same as those employed for the synthesis under atmospheric pressure, though either lower or higher temperatures may be applied the choice dependsol ing, for example, on thev condition of the contact mass, and on the degree of pressure.

In general, lower temperatures will be employed in the case of a fresh contact mass: and of higher pressure, whereas, for lower pressure, or old contact masses, a higher reaction temperature is desirable. The process according to the invention is also applicable to working methods in which a gas circulation is maintained in one or more of the stages.

Example II If a synthesis gas (so-called fresh gas) with the composition:

N2 4%, CO2 2%, CH4 4%, CO 30% and H2 60% be passed at atmospheric pressure over the catalyst described in Example I, and this normal synthesis gas be diluted by returning into circulation the end gases from this pressureless synthesis, a diluted synthesis gas, according to the invention, will be obtained with the approximate` composition z N2 10%, CO2 6%, CHi-l-homologues 17 CO 22% and H2 45% 3 N cubic meufs of fresh gas, the ylem at 12 a1;-

mospheres pressure and 180 C. being 121 grins.,

and at 60 atmospheres and 174 C., as much as 138 grins. per N cubic metre of fresh gas. If the pressure be finally increased to 200 atmospheres, it is advisable to increase the dilution of the gas still further on entering the contact furnace, for example by increasing the amount of end gas introduced into circulation, so that it will have the following approximate-composition:

N2 20%, CO2 13%, CH4 42%, CO 8% and H2 17% With this diluted gas a yield of 148 grms. of liquid hydrocarbons per N cubic metre of fresh gas is obtained by operating at 170 C. with the catalyst in accordance with the same conditions as before.

If, as already mentioned the synthesis gas be diluted by first subjecting an ordinary synthesis gas (with of inert substances) to benzine synthesis, with the known catalysts, at ordinary pressure, the further treatment of the end gas in a second contact stage, under increased pressure in accordance with the invention, may be pel?- formed in a variety of Ways. Both the ordinary pressure portion and the pressure portion of the This is done for example, by occasionally operat- L ing individual elements of the furnace for the pressure portion of the synthesis with the same gas, but under substantially lower pressure, which may .be reduced to that of the atmosphere, and even lower. An excellent regenerative effect is produced in this manner and can be further intensied by passing the expanded gas, during this treatment, through the contact in the direction opposite so that .normally taken by the reaction gas.

It is known to regenerate spent contact masses by steaming. This measure may also be adopted in the process according to the present invention, for example by adding steam, hydrogen, or the like, to the reaction or regenerative gas, for a longer or shorter period in one stage, or part of a stage, of the synthesis, or by employing the said gaseous media separately for steaming. Ac-

cording to the invention, the steaming process .I I

may take place, for example on the contact furnace for the pressure portion, and with or without positive pressure, or in vacuo. In all stages the best effect lis produced by steaming at the lowest possible pressure, or in vacuo, superheated steam being preferably employed and admitted in counteror transverse iiow .to-the normal direction of the reaction gas. Y

In the accompanying drawing, apparatus suitable .for carrying out the process of the present invention are shown diagrammatically.

Fig. 1 shows an apparatus which may be employed for applicant's recirculatory process.

Fig. 2 shows an apparatus in which the catalytic conversion is carried out in two steps, the first of which being carried out under atmossubjected to the catalytic conversion they leave the contact furnace 2 by the conduit 3 and are Vcooled in thercooling means 4. The condensation products are withdrawn through the conduit 5. The cooled gases leave the cooling means 4 through conduit 5 and are Yintroduced into the abor adsorption apparatus 'I for the removal of the more volatile constituents such as benzine and gasoils or by closing valve I and opening valve I2. Such gases are recirculated through the conduits II and 9 with the aid of the suction pump Illa and through conduit IIa into the conduit I. In the latter instance only aportion of the gases is introduced into the abor adsorption apparatus corresponding to the amount of the fresh synthesis gases introduced into conduit I calculated with reference to the contraction which takes place during the catalytic conversion. A corresponding portion of the end gas isl continuously Withdrawn from the ador absorption apparatus through conduit Id when valve I2 is closed and I0 is open and the remainder of the end gas is returned to the contact furnace by means of conduits 8, 9, Ila and I and the suction pump Illa. If only light easily vaporizable hydrocarbonsare formed under the conditions of the conversion, the end gas may be recirculated back to the contact furnace before it reaches the cooling apparatus I through conduits I3, 9, I Ia and I by opening valve IZa.

Conduit I also is provided with the two branch conduits I5 and I8 provided respectively with valves I6 and I9 in order that by suitable setting of valves Il and 20 fresh synthesis gas may be introducedinto the contact furnace at one or more points beyond the point at which the recirculated end gas is introduced therein.

In Fig. 2, the conduit I serves for introducing fresh synthesis gases into the contact furnace 2 which is operated under atmospheric pressure. After the synthesis gases have been subjected to the catalytic conversion, they are withdrawn from the catalytic furnace 2 andn introduced into the cooling apparatus d by conduit 3. The condensation products are Withdrawn through the conduit 5. The remaining gases are Withdrawn from the cooling apparatus I by conduit Ii and are introduced into the compressor I wherein the gases are compressed to the stage desired for the second catalytic conversion. The compressed gases are withdrawn from the compressor 'I and are introduced into the cooling apparatus 9 to then introduced into the ador absorption apparatus I I through conduit Ill to remove the more volatile hydrocarbons which are formed. The end gas obtained from this ador absorption apparatus is then either introduced directly into the second contact furnace through conduits 25 and |40. or is then rst subjected to a Washing with Water under pressure in the column I3 to remove any CO2 present therein by opening valve 3| and closing valve 26 and subsequently introducing into the second contact furnace I5 through conduit I 4a. The end gas may also be introduced into the contact furnace through conduit 29 by opening the valve 30. In the second contact furnace I5 the conversion is carried out Fat higher temperatures and pressures than are employed in the first contact furnace 2. After the catalytic conversion, the products are introduced into the cooling apparatus I1 through conduit I6 and the condensate is Withdrawn through the conduit I8. 'I'he end gas obtained from such cooling apparatus is then either returned directly to the contact furnace I5 through conduits I9, 21, 22, 24 and Ida. with the aid of the suction pump 23 or introduced into the ador absorption apparatus 2l) through conduit I9 valve I9cll being opened and valve 28 closed and then returned to the contact furnace I5 through conduits 2|, 22, 24 and Ma with the aid of the suction pump 23. Conduit 2I also serves for the continuous removal of an amount of end gas from the second conversion substantially equal to the amount of fresh synthesis gas introduced into the second conversion stage from the first conversion stage.

I claim:

l. In the production of hydrocarbons containing more than one carbon atom by the catalytic conversion of carbon monoxide and hydrogen containing gases while maintaining temperatures below 300 C. with catalysts suitable for forming benzine, hydrocarbon oil and parain from such gases at atmospheric pressure and at temperatures below 300 C., said catalysts consisting of hydrogenating metals, diificultly reducible metal compounds and carrier substances, said carrier substances constituting at least half .the weight of the catalysts, the improvement which comprises employing a carbon monoxide and hydrogen containing gas which contains more than 20% of inert constituents and a superatmospheric pressure of above two atmospheres for such conversion.

2. A process according to claim 1 in which the fresh gas is introduced into the catalyst at a point beyond the point at which the recirculated gas is introduced into the catalyst.

3. A process according to claim 1 in which the content of the inert constituents nvsaid gases containing carbon monoxide and hydrogen is' adjusted by the introduction of suchgases occurring as reaction products in said catalytic conversion.

4. In the production of hydrocarbons containing more than one carbon atom by the catalytic conversion of carbon monoxide and 'hydrogen containing gases while maintaining temperatures below 300 C. with catalysts suitable for forming benzine, hydrocarbon oil and parafn from such gases at atmospheric pressure and at temperatures below 300 C., said catalysts consisting of cobalt as a hydrogenating metal, thorium oxide and kieselguhr as a carrier substance, said kieselguhr constituting at least half the weight of the catalysts, the improvement which comprises employing a carbon monoxide and hydrogen containing gas which contains more than 20% of inert constituents and a superatmospheric pressure of above two atmospheres for such conversion.

5. A process for the catalytic conversion of carbon monoxide and hydrogen containing gases to form hydrocarbon containing more than one carbon atom which comprises supplying a fresh gas mixture containing carbon monoxide and hydrogen to a conversion catalyst suitable for forming benzine, hydrocarbon oil and paraftln from such gas at atmospheric pressure and at temperatures below 300 C., said catalyst consisting of hydrogenating metals, diicultly reducible metal compounds and carrier substances, said carrier substances constituting at least one-half ing more than one carbon atom by the catalytic conversion of carbon monoxide and hydrogen containing gases while maintaining temperatures below 300 C. with catalysts suitable for forming benzine, hydrocarbon oil and paraffin from such gases at atmospheric pressure and at temperatures below 300 C., said catalysts consisting of hydrogenating metals, difcultly reducible metal compounds and carrier substances, said carrier substances constituting at least half the weight of the catalysts, the improvement which comprises starting the conversion with an end gas obtained in performing suchl conversion under atmospheric pressure, which end gas contains at least 20% of inert constituents and applying a pressure of above two atmospheres during such conversion of end gas.

'7. A method according to claim 6 in which the pressure applied during the conversion of the end 4gas is suicient that the partial pressure of the carbon monoxide and hydrogen corresponds substantially to the partial 'pressure of such constituents in the original gaseous mixture before conversion v at atmospheric pressure.

8. In the production of hydrocarbons containing more than one carbon atom by the catalytic conversion of carbon monoxide and hydrogen containing gases while maintaining temperatures below 300 C. with catalysts suitable for forming benzine, hydrocarbon oil and parafn from such gases at atmospheric pressure and at temperatures below 300 C., said catalysts consisting of hydrogenating metals, difiicultly reducible metal compounds and carrier substances, said carrier substances constituting at least half the weight of the catalysts, the improvement which comprises performing such catalytic conversion in at 'least two stages, employing atmospheric pressure during the first stage, and employing a pressure of more than two atmospheres and a higher temperature than in the rst stage for the second stage. the second stage being begun when the end gas of said first stage contains at least 20% of inert constituents.

9. A process according to claim ,8 in which a part of the end gas of the laststage is recirculated after removal of at least a part of the reaction products therefrom.

10. In the production of hydrocarbons containing more than one carbon atom by the catalytic conversion of carbon monoxide and hydrogen containing gases while maintaining temperatures below 300 C. with catalysts suitable for forming benzine, hydrocarbon oil and paramn from such gases at atmospheric pressure and at temperatures below 300 C.,` said catalysts consisting of hydrogenating metals, dimcultly re- `ducible metal compounds and carrier substances,

said carrier substances constituting at least half the weight of Athe catalysts, the improvement which comprises employing for such conversion, an end gas of a methanol synthesis from carbon monoxide and hydrogen containing gases, which end gas contains at least 20% of inert constituents, and employing a pressure of more than two atmospheres for such conversion.

i WILHELM HERBERT. 

